This invention relates to certain polyfluoro .gamma.-ketoester compounds and derivatives, to processes for their preparation, and to certain copolymers prepared therefrom.
Wiley, U.S. Pat. No. 2,988,537, discloses a synthesis of certain .beta.-alkoxypolyfluoroketones according to the following sequence: ##STR1## wherein X is halogen, M is an alkali metal and R.sup.1 and R.sup.3 are alkyl or polyfluorinated alkyl groups having up to 18 carbon atoms. R.sup.2 may be hydrogen, an alkyl group or polyfluorinated alkyl group having up to 12 carbon atoms, or an aromatic or arylaliphatic group.
England, U.S. Pat. No. 2,802,028, discloses a process for preparing polyfluoroamides and polyfluorocarboxylic acids of the formula HCXYCF.sub.2 CO.sub.2 M. According to this process, an addition reaction of an alkali metal cyanide and water with fluoroolefins of formula CF.sub.2 .dbd.CXY, followed by hydrolysis, yields the carboxylic acid and amide. In the foregoing formula, X is --F or --Cl, Y is --F, --H, --Cl, an alkyl, cycloalkyl, fluoro- or chloro-substituted alkyl group, and M is an alkali metal.
Selman, U.S. Pat. No. 3,274,239, discloses a process for preparing acyl fluorides of the formula ##STR2## by reacting hexafluoropropene oxide (HFPO) with fluoroketones of formula XR.sub.F C(O)R'.sub.F X', wherein R.sub.F and R'.sub.F are C.sub.1-8 perfluoroalkylene groups, X and X' are hydrogen or halogen, Y is hydroxyl or fluorine, and n is an integer from zero to twenty. Selman also discloses a process for preparation of vinyl ether derivatives by pyrolysis of the corresponding acyl fluoride compounds.
Krespan, U.S. Pat. No. 4,335,255, discloses fluoroketoesters of the formula ##STR3## wherein R is a C.sub.1-8 alkyl group. In addition to a process for preparing the fluoroketoesters, the patent further discloses the reaction of the fluoroketoesters with HFPO to form HFPO adduct acyl fluorides of the formula ##STR4## Pyrolysis of the acyl fluorides in the presence of alkali metal basis salts yields vinyl ethers of formula ##STR5## where X can be selected from CO.sub.2 M, CO.sub.2 R, CO.sub.2 H, COF, COCl, CONH.sub.2 or CN, M is alkali metal, and n is 0 to 6. This patent also describes reaction of the acyl fluorides with perfluoroallyl fluorosulfate, perfluoroallyl fluorochloride or -bromide to yield perfluoroallyl derivatives of the formula ##STR6## where p is 0 to 7, inclusive. Finally, copolymerization of the perfluorovinyl ether and perfluoroallyl ether derivatives with fluorinated vinyl monomers such as tetrafluoroethylene, trifluoroethylene, chlorotrifluoroethylene, or vinylidene fluoride is disclosed.
Sianesi, et al., U.S. Pat. No. 3,847,978, disclose fluoroketoesters of the formula EQU CF.sub.3 C(O)CF.sub.2 [CF(CF.sub.3)CF.sub.2 O].sub.m CF(CF.sub.3)CO.sub.2 R,
and certain copolymers derived therefrom, where R is --H or an alkyl group, and m is an integer between 1 and 50, inclusive.
England, U.S. Pat. No. 4,131,740, discloses .alpha.-carboxylate-.omega.-vinyl ethers of the formula ##STR7## wherein R is a C.sub.1-6 alkyl group, and n is 1-6. Processes for preparing these compounds by pyrolysis of the corresponding acyl fluorides in the presence of Na.sub.2 CO.sub.3 or Na.sub.3 PO.sub.4, and copolymers of the vinyl ethers and such perfluorinated vinyl monomers as tetrafluoroethylene are also described.
McBee, et al., J. Am. Chem. Soc. 75: 3152-3153, discloses a process for synthesizing polyfluoro .beta.-ketoester compounds of formula ##STR8## by a Claisen condensation of polyfluorinated acetate esters using NaH as a condensing agent. R in the foregoing formula can be --H or --C.sub.2 H.sub.5.
Kimoto et al., British Patent Application No. 2,051,831 A, disclose substituted fluorocarbons of formula X(CF.sub.2).sub.n Y, wherein X includes --SR and --SO.sub.2 R substituents and Y can be an acyl halide or vinyl ether substituent, for example: ##STR9## This reference also discloses copolymers of the vinyl ether derivatives and fluorinated olefins, and preparation of ion-exchange membranes from these copolymers which are suitable for use in chlor-alkali electrolysis cells.
Yamabe, et al., U.S. Pat. No. 4,275,226, describe a process for preparing fluorovinyl ether compounds of the formula XR.sub.F CF.sub.2 OCF.dbd.CF.sub.2, wherein X is --H, --Cl, --Br, --F, --CONRR', --COF, --CO.sub.2 R, --SO.sub.2 F or --PO(OR).sub.2, R is a C.sub.1-10 alkyl group, R' is --H or a C.sub.1-10 alkyl group, and R.sub.F is a C.sub.1-20 bifunctional perfluoro-containing group optionally containing one or more ether bonds. According to this process, an iodine-containing polyfluorinated ether compound of formula XR.sub.F CF.sub.2 OCF.sub.2 CF.sub.2 I is reacted with a metallic catalyst to form a fluoro-organometallic compound which is subsequently heated to form the vinyl ether.
Ezzell, et al., U.S. Pat. No. 4,337,211 and European Patent Application (E.P.A.) No. 41,736, disclose compounds having the formula ##STR10## wherein Y can be --SO.sub.2 Z, --C(O)Z, or --P(O)Z.sub.2 ; Z can be --OH, --OA, --F, --Br or --Cl; A is alkali metal, quaternary ammonium or R; R is alkyl or aryl; a and b are 0 or an integer, and R.sub.F and R'.sub.F are each --F, --Cl, perfluoroalkyl or perfluorochloroalkyl. This reference further discloses an ether derivative of the formula ##STR11## wherein X is --F, --Cl, or --Br, or mixtures thereof when n is greater than 1; X' is --Cl or --Br, or mixtures thereof when m is greater than 1; a and b are 0 or an integer, and m and n are 0 or an integer.
Ezzell, et al., U.S. Pat. No. 4,330,654 and E.P.A. Nos. 41,737 and 41,735, disclose vinyl ethers prepared from the aforementioned ether derivative of U.S. Pat. No. 4,337,211 which have the formula ##STR12## as well as certain copolymers derived by reaction of the vinyl ether derivatives with fluorinated olefins.
Finally, Krespan, U.S. Pat. Nos. 4,273,728, 4,273,729 and 4,275,225 each disclose polyfluoroallyl ethers CF.sub.2 .dbd.CFCF.sub.2 OR.sub.F, wherein R.sub.F includes the group [CF.sub.2 CF(CF.sub.3)O].sub.n R.sup.3 Q, where R.sup.3 is a linear or branched perfluoroalkylene group and Q is a functional group including --CO.sub.2 R, where R is a methyl or ethyl group. Fluorinated copolymers of these allyl ether compounds and fluorovinyl monomers are also disclosed.